US4026810A - Intumescent flame retardants - Google Patents
Intumescent flame retardants Download PDFInfo
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- US4026810A US4026810A US05/663,006 US66300676A US4026810A US 4026810 A US4026810 A US 4026810A US 66300676 A US66300676 A US 66300676A US 4026810 A US4026810 A US 4026810A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 61
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 229920000877 Melamine resin Polymers 0.000 claims description 17
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 17
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 16
- -1 phosphorus oxide compound Chemical class 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 11
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 8
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical group CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid group Chemical group C(CCCCC(=O)O)(=O)O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical group OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical group OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001735 carboxylic acids Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N 1-dodecanol group Chemical group C(CCCCCCCCCCC)O LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910009111 xH2 O Inorganic materials 0.000 claims description 3
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims 3
- 125000003158 alcohol group Chemical group 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 239000004033 plastic Substances 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 11
- 235000011007 phosphoric acid Nutrition 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 229920002959 polymer blend Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010348 incorporation Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229960004838 phosphoric acid Drugs 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000012815 thermoplastic material Substances 0.000 description 5
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- REMJSDOVAWDCHS-UHFFFAOYSA-N 2-octylcyclohexan-1-amine Chemical compound CCCCCCCCC1CCCCC1N REMJSDOVAWDCHS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004171 alkoxy aryl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000004367 cycloalkylaryl group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BCQZYUOYVLJOPE-UHFFFAOYSA-N ethane-1,2-diamine;dihydrobromide Chemical compound Br.Br.NCCN BCQZYUOYVLJOPE-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- URMHMMMIVAECEM-UHFFFAOYSA-N octadecan-9-ol Chemical compound CCCCCCCCCC(O)CCCCCCCC URMHMMMIVAECEM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- HRDGAIGDKJXHIU-UHFFFAOYSA-N tetradecan-4-ol Chemical compound CCCCCCCCCCC(O)CCC HRDGAIGDKJXHIU-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
Definitions
- This invention relates to flame retardants. More particularly, this invention relates to a non-halogenated flame retardant suitable for incorporation into synthetic polymers.
- Fire safety rules have increasingly affected the market for flammable plastics.
- Many plastics can be made flame retardant by incorporating therein a halogenated organic material which, on heating, produces an inert gas which dilutes the flammable gases produced by the heated polymer so that they are not within the combustible range.
- a halogenated organic material which, on heating, produces an inert gas which dilutes the flammable gases produced by the heated polymer so that they are not within the combustible range.
- consumer alarm over the possible release of toxic gases during combustion of such flame-retarded plastics has spurred development of other non-halogenated flame retardant additives and flame retardant systems.
- Intumescent flame retardants have been developed as alternatives for the halogenated flame retardants. These flame retardants, upon heating, promote the formation of char which protects the base polymer by providing insulation from heat and oxidative degradation.
- incorporation of intumescent flame retardants within thermoplastics has generally been precluded due to void formation during processing caused by triggering of the gas generating "intumescent reaction" between the components of the flame retardant at processing temperature. Consequently, such intumescent flame retardants must be used as coatings rather than incorporated into the plastics. However, such coatings can be lost if melting of the plastic during combustion carries away the coating from the surface to be protected.
- An intumescent flame retardant has been developed which can be incorporated in a thermoplastic prior to molding.
- This flame retardant is prepared by reacting, for example, phosphoric oxide, phosphoric acid, pentaerythritol and melamine and thereafter curing the reaction product by heating to evolve gaseous products.
- This gas evolving step i.e., curing step, does not fully deplete the gas generating capability of the flame retardant system; thus, at combustion temperatures, further reaction can occur to provide foaming and charring.
- the intumescent flame retardant described above had a moderate to dark brown color after curing. Such color undesirably tints the thermoplastic material into which the intumescent flame retardant is incorporated.
- a method for improving the color of a cured intumescent flame retardant by incorporating therein a color improver compound.
- a cured intumescent flame retardant having improved color.
- the intumescent flame retardant of this invention is a highly cross-linked polymer prepared by the initial condensation of a polyol having from 5 to 15 carbon atoms per molecule and from 4 to 8 hydroxyl groups per molecule with a phosphorus oxide compound of the formula P 2 O 5 .xH 2 O wherein x is a number in the range of 0 to 3, followed by the addition of a nitrogen compound such as melamine and curing.
- the color improver of this invention is added to the composition prior to the curing step. After curing, the mixture is cooled and ground to a particle size suitable for incorporation into thermoplastic materials.
- the intumescent flame retardant described above is improved by incorporating therein at least one color improver of the formula
- R is an organic radical having a valence of z selected from the group consisting of alkyl, cycloalkyl, alkoxy, aryl and combinations thereof such as alkaryl, aralkyl, cycloalkylaryl, aralkoxy, alkoxyaryl and the like, and R' is selected from the group consisting of --H and --R.
- R' groups can be joined to the R group to form a heterocyclic ring.
- suitable alcohol compounds are methanol, 2-ethylhexanol, 4-tetradecanol, 1-octadecanol, carnaubyl alcohol, ethylene glycol, triethylene glycol, benzyl alcohol, cyclohexanol, and the like and mixtures thereof.
- Suitable acids are formic, acetic, pentanoic, adipic, decanoic, stearic, benzoic, p-toluic, dodecanedioic, eicosanoic, cyclopentanecarboxylic, and the like and mixtures thereof.
- Suitable amines are trimethylamine, dibutylamine, 2-ethylhexylamine, octadecylamine, aniline, hexamethylethylenediamine, 2-octylcyclohexylamine, decyldimethylamine, benzylamine, o-tolylamine, piperidine, and the like and mixtures thereof.
- the color improver compounds described above have from 6 to 20 carbon atoms per molecule.
- the radical R is alkyl, alkoxy, cycloalkyl or aralkyl since those compounds in which the functional group Y is attached directly to an aromatic ring generally increase the smoke formation on burning.
- the phosphorus oxide compounds which are suitable for use in the present invention are those compounds having the formula P 2 O 5 .xH 2 O, wherein x has a value of 0 to 3.
- These compounds include, for example, phosphorus pentoxide, orthophosphoric acid, and condensed phosphoric acids having from about 70 to about 99, preferably about 80 to about 90, weight percent, phosphorus pentoxide.
- condensed phosphoric acids can be prepared by a technique known in the art. A mixture of phosphorus pentoxide and orthophosphoric acid has been found to be particularly effective.
- the polyols which are suitable for use in the present invention are saturated, acyclic polyols of 5 to 15 carbon atoms and 4 to 8 hydroxyl groups per molecule.
- the only other functional groups in the polyols are a maximum of two other linkages per molecule.
- suitable polyols include sorbitol, mannitol, pentaerythritol, dipentaerythritol and tripentaerythritol.
- Melamine is generally employed as the nitrogen compound in preparing the intumescent flame retardants of this invention. It will be apparent to those skilled in the art that other nitrogen compounds such as dicyandiamide, urea, dimethylurea and the like, can be used in place of the melamine.
- intumescent flame retardant of this invention is hereinafter described in terms of a mixture of phosphoric acid and phosphorus pentoxide as the phosphorus oxide compound, melamine as the nitrogen compound, and pentaerythritol as the polyol. Accordingly, these ingredients can be combined in amounts as follows:
- the above-described ingredients are combined in any suitable manner, at a temperature and for a time sufficient to provide a composition which, when incorporated into a thermoplastic resin, will impart flame retardant properties to that resin.
- preparation of the flame retardant can be conveniently carried out as follows:
- Step I The phosphoric acid and phosphorus pentoxide are mixed, allowing an autogenous increase in temperature resulting from the exothermic reaction.
- the reaction period can vary broadly from about 5 to 20 minutes.
- Step II The pentaerythritol, the color improver, and about 5-15 percent of the melamine are added, with stirring, to the mixture produced in Step I, at a temperature in the range of 75°-150° C. for about 0.5-8 hours, preferably about 110°-130° C. for about 0.5-4 hours.
- Step III The balance of the melamine is added with stirring, to the mixture produced in Step II.
- the melamine can be added continuously or intermittently over a period of about 0.1-3 hours or more, at a temperature of about 180°-300° C., preferably about 0.1-1.5 hours at about 200°-250° C.
- Step IV The reaction mixture obtained from Step III is cured by continued heating, with stirring, at a temperature of about 200°-300° C. for about 1-5 hours, preferably 240°-270° C. for about 2-3 hours.
- Step V The reaction mixture from Step IV is cooled, then pulverized to a suitable particle size.
- Exclusion of oxygen from the reaction mixture during the curing Step IV and the cooling and pulverizing Step V generally results in a further improvement in color quality of the finished flame retardant.
- Oxygen can be excluded by maintaining an inert atmosphere, such as nitrogen or helium, or by maintaining a reduced pressure over the reaction mixture. It is presently preferred that the entire preparation of the intumescent flame retardant composition be carried out in the absence of oxygen.
- thermoplastic polymers into which the intumescent flame retardant compositions of the present invention can be incorporated include olefin homopolymers, olefin copolymers, styrene resins, acrylonitrile-butadiene-styrene resins, and blends thereof.
- the olefin polymers are prepared from 1-olefins having from 2 to 8 carbon atoms per molecule.
- the flame retardant compositions are particularly suitable for incorporation into normally solid molding grade olefin polymer resins.
- thermoplastic polymers suitable for use in the present invention are polyethylene, polypropylene, copolymers of propylene with minor amounts of ethylene, copolymers of ethylene with minor amounts of other 1-olefins such as 1-butene or 1-hexene, copolymers containing substantial amounts of ethylene and propylene having some elastomeric character such as ethylene-propylene rubber (EPR), polystyrene, terpolymers of acrylonitrile-butadiene-styrene and the like and blends thereof.
- EPR ethylene-propylene rubber
- the flame retardant compositions are incorporated into the thermoplastic polymers using any convenient method which will uniformly distribute the flame retardant composition throughout the plastic and impact flame retardant properties thereto. This can be accomplished by conventional milling procedures in which the flame retardant composition is milled into the plastic at or above the softening or melting point of the plastic, such as by hot roll mills or heated internal mixers.
- the amount of flame retardant composition incorporated into the thermoplastic material will be that amount sufficient to achieve the degree of flame retardancy desired. Since the response to the flame retardant composition may vary with the specific thermoplastic material into which it is incorporated, the amount of flame retardant will generally be within the range of about 10 to about 50 parts by weight per 100 parts of thermoplastic material.
- the balance of the melamine was then added, in small portions with stirring, as the temperature was raised over a period of about 1 hour to about 250° C.
- the reaction mixture was then maintained at a temperature of about 250°-265° C. for 2-3 hours during whichtime curing of the flame retardant composition took place.
- Runs 1-3 in Table I illustrate typical results obtained in the absence of aggregater improver.
- the color of such preparation is generally dark ranging from a tan to a brown.
- Runs 4-11 illustrate the results obtained when various amounts of long-chain alcohol color improvers are incorporated into the flame retardant composition. While varying slightly from batch to batch the color of these invention runs is seen to be significantly lighter thanthat of control runs 1-3. Similarly, invention runs 12-18 which employ various longchain carboxylic acids are also shown to produce flame retardant compositions of a lighter color than that of control runs 1-3. In invention runs 19-20, the long-chain amine, octadecylamine, is also shown to be effective in reducing color in the flame retardant composition.
- compositions shown in Table I were incorporated into a polymer blend consisting of 42.5% polypropylene (12 melt flow), 30% polyethylene (18 melt flow) and 27.5% of a commercial ethylene-propylene-rubber (Exxon Vistalon 606 EPR), by weight and tested for fire retardancy as well as being examined for color.
- the flame retardant compositions were incorporated into the polymer blend by mixing on a steam-heated roll mill maintained at about 168°-178° C. The polymers were blended together on the roll mill first. The flame retardant composition was then slowly milled into the polymer blend. After completion of the addition of the flame retardant, the milling was continued for 4.5 minutes to disperse the retardant throughout the polymer.
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Abstract
The color of a cured intumescent flame retardant is improved by incorporating a suitable alcohol, carboxylic acid or amine into the composition prior to curing the composition.
Description
This invention relates to flame retardants. More particularly, this invention relates to a non-halogenated flame retardant suitable for incorporation into synthetic polymers.
Fire safety rules have increasingly affected the market for flammable plastics. Many plastics can be made flame retardant by incorporating therein a halogenated organic material which, on heating, produces an inert gas which dilutes the flammable gases produced by the heated polymer so that they are not within the combustible range. However, consumer alarm over the possible release of toxic gases during combustion of such flame-retarded plastics has spurred development of other non-halogenated flame retardant additives and flame retardant systems.
Intumescent flame retardants have been developed as alternatives for the halogenated flame retardants. These flame retardants, upon heating, promote the formation of char which protects the base polymer by providing insulation from heat and oxidative degradation. However, incorporation of intumescent flame retardants within thermoplastics has generally been precluded due to void formation during processing caused by triggering of the gas generating "intumescent reaction" between the components of the flame retardant at processing temperature. Consequently, such intumescent flame retardants must be used as coatings rather than incorporated into the plastics. However, such coatings can be lost if melting of the plastic during combustion carries away the coating from the surface to be protected.
An intumescent flame retardant has been developed which can be incorporated in a thermoplastic prior to molding. This flame retardant is prepared by reacting, for example, phosphoric oxide, phosphoric acid, pentaerythritol and melamine and thereafter curing the reaction product by heating to evolve gaseous products. This gas evolving step, i.e., curing step, does not fully deplete the gas generating capability of the flame retardant system; thus, at combustion temperatures, further reaction can occur to provide foaming and charring.
It was found, however, that the intumescent flame retardant described above, had a moderate to dark brown color after curing. Such color undesirably tints the thermoplastic material into which the intumescent flame retardant is incorporated.
Accordingly, it is an object of this invention to provide a cured intumescent flame retardant of improved color.
Other objects, aspects and advantages of this invention will be apparent to those skilled in the art from a reading of the following disclosure and appended claims.
In accordance with the present invention, it has now been found that undesirable color formation during the preparation of a cured intumescent flame retardant can be minimized by blending with the retardant composition, prior to curing, a minor amount of a suitable alcohol, carboxylic acid or amine color improver compound.
Thus, according to the present invention, there is provided a method for improving the color of a cured intumescent flame retardant by incorporating therein a color improver compound. There is also provided a cured intumescent flame retardant having improved color.
The intumescent flame retardant of this invention is a highly cross-linked polymer prepared by the initial condensation of a polyol having from 5 to 15 carbon atoms per molecule and from 4 to 8 hydroxyl groups per molecule with a phosphorus oxide compound of the formula P2 O5.xH2 O wherein x is a number in the range of 0 to 3, followed by the addition of a nitrogen compound such as melamine and curing. The color improver of this invention is added to the composition prior to the curing step. After curing, the mixture is cooled and ground to a particle size suitable for incorporation into thermoplastic materials.
The intumescent flame retardant described above is improved by incorporating therein at least one color improver of the formula
R-- Y.sub.z
having 1 to 25 carbon atoms per molecule, wherein Y is selected from the group consisting of --OH, --COOH and --NR'2, z is a number having a value of 1, 2 or 3, R is an organic radical having a valence of z selected from the group consisting of alkyl, cycloalkyl, alkoxy, aryl and combinations thereof such as alkaryl, aralkyl, cycloalkylaryl, aralkoxy, alkoxyaryl and the like, and R' is selected from the group consisting of --H and --R. One of the R' groups can be joined to the R group to form a heterocyclic ring.
Some specific examples of suitable alcohol compounds are methanol, 2-ethylhexanol, 4-tetradecanol, 1-octadecanol, carnaubyl alcohol, ethylene glycol, triethylene glycol, benzyl alcohol, cyclohexanol, and the like and mixtures thereof.
Some specific examples of suitable acids are formic, acetic, pentanoic, adipic, decanoic, stearic, benzoic, p-toluic, dodecanedioic, eicosanoic, cyclopentanecarboxylic, and the like and mixtures thereof.
Some specific examples of suitable amines are trimethylamine, dibutylamine, 2-ethylhexylamine, octadecylamine, aniline, hexamethylethylenediamine, 2-octylcyclohexylamine, decyldimethylamine, benzylamine, o-tolylamine, piperidine, and the like and mixtures thereof.
Those skilled in the art will appreciate that those alcohols, acids or amines of relatively low molecular weight require closed systems to prevent their loss before they can be chemically incorporated into the flame retardant composition.
In a presently preferred embodiment, the color improver compounds described above have from 6 to 20 carbon atoms per molecule. In a more preferred embodiment, the radical R is alkyl, alkoxy, cycloalkyl or aralkyl since those compounds in which the functional group Y is attached directly to an aromatic ring generally increase the smoke formation on burning.
The phosphorus oxide compounds which are suitable for use in the present invention are those compounds having the formula P2 O5.xH2 O, wherein x has a value of 0 to 3. These compounds include, for example, phosphorus pentoxide, orthophosphoric acid, and condensed phosphoric acids having from about 70 to about 99, preferably about 80 to about 90, weight percent, phosphorus pentoxide. Such condensed phosphoric acids can be prepared by a technique known in the art. A mixture of phosphorus pentoxide and orthophosphoric acid has been found to be particularly effective.
The polyols which are suitable for use in the present invention are saturated, acyclic polyols of 5 to 15 carbon atoms and 4 to 8 hydroxyl groups per molecule. Preferably, in addition to the carbon, hydrogen and hydroxyl groups, the only other functional groups in the polyols are a maximum of two other linkages per molecule. Examples of suitable polyols include sorbitol, mannitol, pentaerythritol, dipentaerythritol and tripentaerythritol.
Melamine is generally employed as the nitrogen compound in preparing the intumescent flame retardants of this invention. It will be apparent to those skilled in the art that other nitrogen compounds such as dicyandiamide, urea, dimethylurea and the like, can be used in place of the melamine.
The above-described ingredients which are suitable for use in preparing the flame retardant composition of this invention are combined in amounts as follows:
______________________________________ Parts by Weight per 100 parts by Weight of Reaction Mixture Ingredient Broad Preferred ______________________________________ Phosphorus oxide Compound 10-75 15-50 Polyol 5-40 10-25 Nitrogen compound 10-70 15-50 Color improver 0.5-20 2-10 ______________________________________
Preparation of the intumescent flame retardant of this invention is hereinafter described in terms of a mixture of phosphoric acid and phosphorus pentoxide as the phosphorus oxide compound, melamine as the nitrogen compound, and pentaerythritol as the polyol. Accordingly, these ingredients can be combined in amounts as follows:
______________________________________ Parts by Weight per 100 parts by Weight of Reaction Mixture Ingredient Broad Preferred ______________________________________ Phosphoric acid 0.5-25 5-15 Phosphorous pentoxide 10-75 15-50 Pentaerythritol 5-30 10-25 Melamine 10-70 15-50 Color improver 0.5-20 2-10 ______________________________________
To prepare the intumescent flame retardant composition, the above-described ingredients are combined in any suitable manner, at a temperature and for a time sufficient to provide a composition which, when incorporated into a thermoplastic resin, will impart flame retardant properties to that resin. Generally, preparation of the flame retardant can be conveniently carried out as follows:
Step I: The phosphoric acid and phosphorus pentoxide are mixed, allowing an autogenous increase in temperature resulting from the exothermic reaction. The reaction period can vary broadly from about 5 to 20 minutes.
Step II: The pentaerythritol, the color improver, and about 5-15 percent of the melamine are added, with stirring, to the mixture produced in Step I, at a temperature in the range of 75°-150° C. for about 0.5-8 hours, preferably about 110°-130° C. for about 0.5-4 hours.
Step III: The balance of the melamine is added with stirring, to the mixture produced in Step II. The melamine can be added continuously or intermittently over a period of about 0.1-3 hours or more, at a temperature of about 180°-300° C., preferably about 0.1-1.5 hours at about 200°-250° C.
Step IV: The reaction mixture obtained from Step III is cured by continued heating, with stirring, at a temperature of about 200°-300° C. for about 1-5 hours, preferably 240°-270° C. for about 2-3 hours.
Step V: The reaction mixture from Step IV is cooled, then pulverized to a suitable particle size.
Exclusion of oxygen from the reaction mixture during the curing Step IV and the cooling and pulverizing Step V generally results in a further improvement in color quality of the finished flame retardant. Oxygen can be excluded by maintaining an inert atmosphere, such as nitrogen or helium, or by maintaining a reduced pressure over the reaction mixture. It is presently preferred that the entire preparation of the intumescent flame retardant composition be carried out in the absence of oxygen.
The thermoplastic polymers into which the intumescent flame retardant compositions of the present invention can be incorporated include olefin homopolymers, olefin copolymers, styrene resins, acrylonitrile-butadiene-styrene resins, and blends thereof. The olefin polymers are prepared from 1-olefins having from 2 to 8 carbon atoms per molecule. The flame retardant compositions are particularly suitable for incorporation into normally solid molding grade olefin polymer resins.
Examples of normally solid thermoplastic polymers suitable for use in the present invention are polyethylene, polypropylene, copolymers of propylene with minor amounts of ethylene, copolymers of ethylene with minor amounts of other 1-olefins such as 1-butene or 1-hexene, copolymers containing substantial amounts of ethylene and propylene having some elastomeric character such as ethylene-propylene rubber (EPR), polystyrene, terpolymers of acrylonitrile-butadiene-styrene and the like and blends thereof.
The flame retardant compositions are incorporated into the thermoplastic polymers using any convenient method which will uniformly distribute the flame retardant composition throughout the plastic and impact flame retardant properties thereto. This can be accomplished by conventional milling procedures in which the flame retardant composition is milled into the plastic at or above the softening or melting point of the plastic, such as by hot roll mills or heated internal mixers.
The amount of flame retardant composition incorporated into the thermoplastic material will be that amount sufficient to achieve the degree of flame retardancy desired. Since the response to the flame retardant composition may vary with the specific thermoplastic material into which it is incorporated, the amount of flame retardant will generally be within the range of about 10 to about 50 parts by weight per 100 parts of thermoplastic material.
Other conventional additives such as pigments, fillers, antioxidants, and the like can also be incorporated into the final composition. Additionally, other flame retardant compositions or flame retardant adjuvants such as antimony oxide, ethylene diamine dihydrobromide and the like can also be present.
The following examples illustrate the invention:
In each of the flame retardant preparation runs tabulated below, phosphoricacid (85%) was added slowly, with stirring, to phosphorus pentoxide. The moderate flow of nitrogen was kept over the mixture at all times. A mixture of pentaerythritol, the indicated color improver compound, and 5-15 weight percent of the total amount of melamine was then added, in small increments, also with stirring. The temperature of the reaction mixture was raised to about 120° C. and maintained there for about 3 hours.
The balance of the melamine was then added, in small portions with stirring, as the temperature was raised over a period of about 1 hour to about 250° C. The reaction mixture was then maintained at a temperature of about 250°-265° C. for 2-3 hours during whichtime curing of the flame retardant composition took place.
When the reaction mixture was adequately cooled, generally after standing overnight still under a flow of nitrogen, it was removed from the reactionand pulverized in a blender to pass through an 80-mesh sieve. The essentialconditions and results of these runs are shown in Table I.
Table I __________________________________________________________________________ Preparation of Intumescent Flame Retardants P.sub.2 O.sub.5 H.sub.3 PO.sub.4 (85%) Pentaerythritol, Melamine, Color Improver, Product Run No. g g g g g g Color __________________________________________________________________________ 1 141 46.5 81.6 151.5 none 360 brown 2 141 46.5 81.6 151.5 none 369 tan 3 141 46.5 81.6 151.5 none 365 dk. tan 4 141 46.5 74.1 151.5 ODA, 15 400 off-white 5 141 46.5 79.7 151.5 ODA, 15 410 off-white 6 141 46.5 72.1 151.5 ODA, 75 438 lt. tan 7 141 46.5 78.7 151.5 ODA, 15 348 off-white 8 141 46.5 81.6 151.5 ODA, 15 408 v. lt. tan 9 141 46.5 79.7 151.5 ODA, 15 411 off-white 10 141 46.5 74.7 151.5 ODA, 15 382 tan LA, 15 11 141 46.5 73.0 151.5 ODA, 15 415 lt. tan TEG, 15 12 141 46.5 81.6 151.5 SA, 15 413 off-white 13 141 46.5 81.6 151.5 SA, 15 410 v. lt. tan 14 141 45.8 81.6 151.5 SA, 15 345 off-white 15 141 45.4 81.6 151.5 SA, 15 317 lt. tan DiC.sub.12, 15 16 141 45.4 81.6 151.5 SA, 15 415 yellow-tan AA, 15 17 142 46.5 81.6 151.5 SA, 25 403 tan 18 142 46.5 81.6 151.5 SA, 15 414 off-white 19 141 46.5 81.6 151.5 OAM, 15 417 off-white 20 141 46.5 81.6 151.5 OAM, 15 419 lt. tan __________________________________________________________________________ ODA = Octadecanol TEG = Triethylene Glycol DiC.sub.12 = Dodecanedioic Acid LA = Lauryl Alcohol SA = Stearic Acid AA = Adipic Acid OAM = Octadecylamine
Runs 1-3 in Table I illustrate typical results obtained in the absence of acolor improver. The color of such preparation is generally dark ranging from a tan to a brown.
Runs 4-11, on the other hand, illustrate the results obtained when various amounts of long-chain alcohol color improvers are incorporated into the flame retardant composition. While varying slightly from batch to batch the color of these invention runs is seen to be significantly lighter thanthat of control runs 1-3. Similarly, invention runs 12-18 which employ various longchain carboxylic acids are also shown to produce flame retardant compositions of a lighter color than that of control runs 1-3. In invention runs 19-20, the long-chain amine, octadecylamine, is also shown to be effective in reducing color in the flame retardant composition.
To illustrate that color improvements of the flame retardant composition would carry through into the resin into which the composition was incorporated with no loss of flame retardancy, several compositions shown in Table I were incorporated into a polymer blend consisting of 42.5% polypropylene (12 melt flow), 30% polyethylene (18 melt flow) and 27.5% ofa commercial ethylene-propylene-rubber (Exxon Vistalon 606 EPR), by weight and tested for fire retardancy as well as being examined for color.
The flame retardant compositions were incorporated into the polymer blend by mixing on a steam-heated roll mill maintained at about 168°-178° C. The polymers were blended together on the roll mill first. The flame retardant composition was then slowly milled into the polymer blend. After completion of the addition of the flame retardant, the milling was continued for 4.5 minutes to disperse the retardant throughout the polymer.
After hot roll milling, a portion of the polymer blend containing the flameretardant composition, was compression-molded into "picture frame" molds. Approximately 25g of the retarded polymer blend was placed in a 5 inch by 2.5 inch by 1/8 inch frame and heated to about 177° C. under about 25 tons platen pressure. These samples were cut into 5 inch by 1/2 inch strips for UL-94 tests. Two of these strips were further cut into 5 inch by 1/4 inch strips for oxygen index (O.I.) tests.
The essential conditions and results of these tests are shown in Table II below:
Table II ______________________________________ Performance of Flame Retardants in Polymer Blends Flame Retardant Polymer Blend Run Color Loading Blend Flame Retardancy No..sup.a Improver phr Color UL-94.sup.b O.I..sup.c ______________________________________ 2 None 40 dk. V-O 26.0 brown 9 Octadecanol 40 lt. tan V-O 27.8 18 Stearic Acid 40 lt. tan V-O 28.0 20 Octadecylamine 40 tan V-O 26.0 ______________________________________ .sup.a Refers to Run Nos. of Table I.? .sup.b Underwriters Laboratory Bulletin 94 (UL-94), Vertical Burning Test See also Modern Plastics, October 1970, p. 92 and see also Modern Plastics Encyclopedia, e.g., 1973-74, Vol. 50, No. 10A, p. 655A. A rating of V-O means burning of specimen ceases in 5 seconds or less and releases no flaming particles or drops. .sup.c Oxygen Index Test. See Modern Plastics, p. 141, Nov. 1966. Briefly this is a measure of the minimum percentage of oxygen required in an oxygen-nitrogen mixture that will just sustain combustion of a vertically mounted specimen that has been ignited at its upper end. Thus, high O.I. values are desirable.
Examinations of data in Table II clearly show that the incorporation of these alcohols, acids, or amines into the flame retardant composition not only improved the color of the flame retardant but also improved the colorof the polymer compositions into which the retardants were subsequently incorporated. Moreover, it is seen from the UL-94 and O.I. tests that thisimprovement in color was obtained at no sacrifice of flame retardant properties for the final composition.
Reasonable variations and modifications, which will be apparent to those skilled in the art, can be made in this invention without departing from the spirit and scope thereof.
Claims (29)
1. A method for improving the color of a cured intumescent flame retardant composition comprising (A) the initial condensation of a polyol having from 5 to 15 carbon atoms per molecule and from 4 to 8 hydroxyl groups per molecule in an approximate amount ranging from 5 to 40 parts with a phosphorus oxide compound of the formula P2 O5.xH2 O wherein x is a number in the range of 0 to 3 in an approximate amount ranging from 10 to 75 parts, in the presence of 5 to 15 percent of an approximate amount ranging from 10 to 70 parts of a nitrogen compound selected from the group consisting of melamine, dicyandiamide, urea and dimethylurea, and a color improving amount of a color improving compound; (B) the addition to the mixture of step (A) of the balance of said nitrogen compound over a period of about 0.1-3 hours or more at a temperature of about 180°-300° C.; and (C) thereafter curing by heating the reaction mixture of step (B) to evolve gaseous products, said color improving compound being of the formula R--Yz having from 1 to 25 carbon atoms per molecule, wherein Y is selected from the group consisting of --OH, --COOH and --NR'2, z is a number having a value of 1, 2 and 3, R is an organic radical having a valence z selected from the group consisting of alkyl, cycloalkyl, alkoxy, aryl and combinations thereof, and R' is selected from the group consisting of --H and --R, wherein one of said R' groups can be joined with said R group to form a heterocyclic ring.
2. The method of claim 1 wherein said color improver has from 6 to 20 carbon atoms per molecule.
3. The method of claim 1 wherein said color improver has from 6 to 20 carbon atoms per molecule and said R is alkyl.
4. The method of claim 1 wherein said color improver is a carboxylic acid.
5. The method of claim 1 wherein said color improver is an alcohol.
6. The method of claim 1 wherein said color improver is an amine.
7. The method of claim 1 wherein said phosphorus oxide compound is employed in an approximate amount ranging from 10 to 75 parts, said nitrogen compound is employed in an approximate amount ranging from 10 to 70 parts, said polyol is employed in an approximate amount ranging from 5 to 40 parts and said color improving compound is employed in an approximate amount ranging from 0.5 to 20 parts.
8. The method of claim 7 wherein said phosphorus oxide compound is a mixture of phosphoric acid and phosphorus pentoxide, said polyol is pentaerythritol and said nitrogen compound is melamine.
9. The method of claim 1 wherein said color improving compound is octadecanol.
10. The method of claim 1 wherein said color improver is lauryl alcohol.
11. The method of claim 1 wherein said color improver is triethylene glycol.
12. The method of claim 1 wherein said color improver is stearic acid.
13. The method of claim 1 wherein said color improver is dodecanedioic acid.
14. The method of claim 1 wherein said color improver is adipic acid.
15. The method of claim 1 wherein said color improver is octadecyl amine.
16. The method of claim 8 wherein
(A) said phosphoric acid and said phosphorus pentoxide are mixed, allowing an autogenous increase in temperature.
(B) said pentaerythritol, said color improver and the portion of said melamine are added, with stirring, to the mixture produced in step (A), at a temperature in the range of 75°-150° C. for about 0.5-8 hours,
(C) the balance of said melamine is added, with stirring, to the mixture produced in step (B) over a period of about 0.1-3 hours at a temperature of about 180°-300° C.,
(d) the reaction mixture obtained from step (C) is cured by continued heating, with stirring at a temperature of about 200°-300° C. for about 1-5 hours, and
(E) the reaction mixture from step (D) is cooled, then pulverized to a suitable particle size.
17. A cured intumescent flame retardant prepared according to the method of claim 25.
18. The product of claim 17 wherein said phosphorus oxide compound is employed in an approximate amount ranging from 10 to 75 parts, said nitrogen compound is employed in an approximate amount ranging from 10 to 70 parts, said polyol is employed in an approximate amount ranging from 5 to 40 parts and said color improver is employed in an approximate amount ranging from 0.5 to 20 parts.
19. The product of claim 18 wherein said phosphorus oxide compound is a mixture of phosphoric acid and phosphorus pentoxide and said polyol is pentaerythritol, and said nitrogen compound is melamine.
20. The product of claim 17 wherein said color improver is an alcohol.
21. The product of claim 17 wherein said color improver is a carboxylic acid.
22. The product of claim 17 wherein said color improver is an amine.
23. The product of claim 20 wherein said color improver is octadecanol.
24. The product of claim 20 wherein said color improver is lauryl alcohol.
25. The product of claim 20 wherein said color improver is triethylene glycol.
26. The product of claim 21 wherein said color improver is stearic acid.
27. The product of claim 21 wherein said color improver is dodecanedioic acid.
28. The product of claim 21 wherein said color improver is adipic acid.
29. The product of claim 22 wherein said color improver is octadecylamine.
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Cited By (25)
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US4096113A (en) * | 1974-07-15 | 1978-06-20 | Phillips Petroleum Company | Flame retardant polyolefins |
US4115349A (en) * | 1977-08-03 | 1978-09-19 | Phillips Petroleum Company | Triphenylphosphine oxide as a promoter for phosphorus-containing flame retardant |
US4136082A (en) * | 1976-02-13 | 1979-01-23 | Phillips Petroleum Company | Flame-retardant polyolefins |
US4144385A (en) * | 1976-11-27 | 1979-03-13 | British Industrial Plastics Limited | Intumescent coating materials |
US4155900A (en) * | 1978-09-06 | 1979-05-22 | Phillips Petroleum Company | Flame retardants for synthetic resins |
US4195115A (en) * | 1976-11-27 | 1980-03-25 | British Industrial Plastics Limited | Coating compositions |
US4201593A (en) * | 1978-12-06 | 1980-05-06 | Velsicol Chemical Corporation | Novel intumescent composition |
US4210452A (en) * | 1978-12-06 | 1980-07-01 | Veesicol Chemical Corporation | Novel intumescent composition |
US4221837A (en) * | 1979-09-17 | 1980-09-09 | Velsicol Chemical Corporation | Flame retardant article |
US4226907A (en) * | 1979-09-17 | 1980-10-07 | Velsicol Chemical Corporation | Flame retardant article |
US4241145A (en) * | 1979-09-17 | 1980-12-23 | Velsicol Chemical Corporation | Novel intumescent composition |
US4312805A (en) * | 1977-01-12 | 1982-01-26 | Montedison, S.P.A. | Self-extinguishing polymer compositions |
US4328139A (en) * | 1980-10-27 | 1982-05-04 | E. I. Du Pont De Nemours And Company | Flame retardant filled polypropylene compositions containing carbon black and a cured intumescent flame retardant (IFR) |
US5132054A (en) * | 1991-05-16 | 1992-07-21 | Specified Technologies Inc. | Composition of matter for a fire retardant intumescent material having two stages of expansion and a process for making thereof |
EP0551855A1 (en) * | 1992-01-10 | 1993-07-21 | FLAM-X Gesellschaft für Brandschutz Technologie mbH & Co. KG | Flame-retardant composition |
US6090316A (en) * | 1998-05-01 | 2000-07-18 | J. M. Huber Corporation | Melamine and aluminum hydroxide blend and method for making and using the same |
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US4155900A (en) * | 1978-09-06 | 1979-05-22 | Phillips Petroleum Company | Flame retardants for synthetic resins |
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US6090316A (en) * | 1998-05-01 | 2000-07-18 | J. M. Huber Corporation | Melamine and aluminum hydroxide blend and method for making and using the same |
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US20050287894A1 (en) * | 2003-07-03 | 2005-12-29 | John Burns | Articles of enhanced flamability resistance |
US20060029836A1 (en) * | 2004-08-06 | 2006-02-09 | George Hairston | Mattress with top panel incorporating foam of enhanced flammability resistance |
US20060030227A1 (en) * | 2004-08-06 | 2006-02-09 | George Hairston | Intumescent flame retardent compositions |
US20060030645A1 (en) * | 2004-08-06 | 2006-02-09 | George Hairston | Mattress side panels incorporating foam of enhanced flammability resistance |
US20060046591A1 (en) * | 2004-08-31 | 2006-03-02 | George Hairston | Mattress covers of enhanced flammability resistance |
US20070186353A1 (en) * | 2006-02-10 | 2007-08-16 | Xinggao Fang | Fire resistant fabric formed from treated fibers |
CN102585293A (en) * | 2011-01-14 | 2012-07-18 | 中国林业科学研究院木材工业研究所 | Flame retardant, and preparation method and application thereof |
CN102585293B (en) * | 2011-01-14 | 2013-10-16 | 中国林业科学研究院木材工业研究所 | Flame retardant, and preparation method and application thereof |
US20170016148A1 (en) * | 2014-03-11 | 2017-01-19 | Smartpolymer Gmbh | Flame-resistant molded cellulose bodies produced according to a direct dissolving method |
US10443153B2 (en) * | 2014-03-11 | 2019-10-15 | Smartpolymer Gmbh | Flame-resistant molded cellulose bodies produced according to a direct dissolving method |
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